CN102256600A - 陶瓷蜂窝结构体表面涂层 - Google Patents

陶瓷蜂窝结构体表面涂层 Download PDF

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CN102256600A
CN102256600A CN2009801505994A CN200980150599A CN102256600A CN 102256600 A CN102256600 A CN 102256600A CN 2009801505994 A CN2009801505994 A CN 2009801505994A CN 200980150599 A CN200980150599 A CN 200980150599A CN 102256600 A CN102256600 A CN 102256600A
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coating material
inorfil
fiber
inorganic
fibre
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CN102256600B (zh
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J·A·费尔南多
K·B·米勒
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Unifrax 1 LLC
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Unifrax Corp
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Abstract

一种多孔陶瓷(蜂窝)结构体表面涂层，和一种生产多孔陶瓷结构体表面涂层的方法，其提供硬壳、坚固、耐酸和耐碱、耐切屑的陶瓷蜂窝结构体涂层，其可阻挡污染控制催化剂被吸收进表面涂层。

Description

陶瓷蜂窝结构体表面涂层
背景技术
陶瓷蜂窝结构体，例如那些用作催化转换器和柴油微粒过滤器(“DPFs”)的，可通过多种方法来生产。通常，通过挤出来生产蜂窝结构体，得到由蜂窝结构体的壁所分割的多种贯通孔或通道。每一条通道在该结构体的进料口尾端或出料口尾端封闭，并且在高温烧结该结构体。可选择地盖住邻近通道，以形成万格盘式样，从而迫使进入该结构体的流体在流出该结构体之前，流经结构体的壁。在这种方式中，流经该结构体的流体，当该流体流经该蜂窝结构体的壁时，可以与催化剂接触或过滤流体中的颗粒。
在催化剂转换器中与那些蜂窝结构体配合使用的催化剂，要求蜂窝壁的高温和高孔隙率，以保证催化剂的效率。因此，需要该结构体可被快速加热，以便有效清洁来自刚启动的引擎的废气。由于通常在废气先流经DPF、后流经独立的催化剂转换器的情况下使用DPFs，所以用作DPFs的那些结构体，要求当废气流经该过滤器时具有低压力损耗。
因此，希望这些蜂窝体结构，在可以忍受与内燃机相关联的极端温度的同时，具有低热容，使得经过该结构体的压力损失最小化。为了获得上述性质，希望获得高孔隙率和低壁厚。然而，高孔隙率和低壁厚导致低机械强度，从而导致在制造中产生多种问题。
在解决这些问题的一项尝试中，本领域现公开的方法是蜂窝结构体置于陶瓷糊料或衬垫之内，使得结构体具有增强的机械强度，避免震动，并封闭该结构体，从而当其外壳密封时，废气将不会在该结构体和其外壳之间流过。
同样已提出通过制造多个较小的蜂窝结构体、并利用陶瓷粘合材料将其粘结在一起的方法制造一种单一结构体，其仍需要利用在结构体外表面周围的表面涂层来保证外表面的一致性。这些单一的蜂窝结构体可更有效支撑它们的自重，并且一旦烧结该整体，该粘合材料可使得该结构体的机械强度得到增强。
无论该整体是通过较小蜂窝结构体组装得到，还是作为单一元件挤出得到，在烧结步骤之后，该结构体的外表面可能需要切削加工，使得该结构体外形满足关于粗糙度和实际直径的严格规范性要求，并产生可供粘结表面涂层的表面。在某些情况下，这种切削加工会导致部分蜂窝单元暴露，从而需要由表面涂层填充，在这些情况下通常是陶瓷糊料。
表面涂层优选包括陶瓷糊料，这是因为它们可采用与该陶瓷蜂窝结构体类似的材料制作，使得其热容相近，并且它们可用于完善该结构体的外形。可与糊料结合使用衬垫，以便于在使用该结构体时，对其提供额外保护使其免于震动损伤。优选地，这些糊料通过吸收酸性催化物质，将抗裂化、剥落和退化。现有的陶瓷糊料材料中，没有一种能充分实现上述所有目的。
附图简要说明
图1是受试表面涂层配方实施例与商用陶瓷糊料表面涂层产品相比较的压坯密度的图形表示。
图2是受试表面涂层配方实施例与商用陶瓷糊料表面涂层产品相比较的粘度的图形表示。
图3是受试表面涂层配方实施例与商用陶瓷糊料表面涂层产品相比较的在多种条件下的断裂模量的图形表示。
详细说明
现在我们已经表明了在制造陶瓷蜂窝结构体的干燥和烧结阶段，添加二次纤维可最小化该表面涂层的裂化。这些二次纤维不是必须是耐高温纤维，不具备耐特别高温度功能的纤维亦可非常好地防止该表面涂层在干燥和烧结阶段的裂化。该术语“蜂窝结构体”包括任何用于废气处理装置，例如催化剂转换器、柴油颗粒过滤器、选择性催化还原装置、NOx捕获器及类似装置中的多孔陶瓷结构体。
进一步，我们已经表明了，在干燥阶段，如本文所述的表面涂层的表面上形成非吸附的、坚硬的、致密的、类似于蛋壳的表面。而在理论上没有被限制的是，可以相信在干燥阶段，由二氧化硅类的迁移形成该表面。该表面防止酸性催化剂涂层被吸附进该表面涂层。优选的是防止吸收，因为，如上所述，通过暴露于酸性催化剂涂层下，可退化该表面涂层。防止吸收同样允许使用较少量的催化剂涂层，降低了整体产品的成本。
本文提供的是陶瓷蜂窝结构体表面涂层，和生产陶瓷蜂窝结构体表面涂层的方法，其提供硬壳的、耐酸和耐碱的、耐切削的具有高强度的陶瓷蜂窝结构体表面涂层，并且其可阻挡污染控制催化剂被吸收进表面涂层。
在一个实施方案中，用于多孔陶瓷(例如，蜂窝)基体的陶瓷表面涂层材料包括耐火陶瓷纤维或生物可溶性无机纤维；粘度调节剂、胶态无机氧化物；任选地，无机粘合剂；任选地，无机微粒；和任选地，二次无机纤维。
该耐火陶瓷纤维或生物可溶性无机纤维可包括铝硅酸盐纤维、碱土金属硅酸盐纤维、或铝酸钙纤维中的至少一种。该耐火陶瓷纤维(RCF)可包括但不限于铝硅酸盐纤维。该碱土金属硅酸盐纤维可包括但不限于硅酸镁纤维或硅酸钙镁纤维。
这些主要纤维(RCF或生物可溶性无机纤维)可以以不同程度的粒含量来应用，从“原样的”(如所生产的)至高系数和空气分类纤维，在其中充分地移除所有粒。在某些实施方式中，可以球磨该主要纤维。
该粘度调节剂可以包括但不限制于：烷基纤维素聚合物，例如甲基纤维素(MC)和/或其衍生物，例如羟丙基甲基纤维素(HPMC)，羟乙基甲基纤维素(HEMC)，羟乙基纤维素(HEC)，羧甲基纤维素(CMC)，羟乙基羧甲基纤维素(HECMC)，或羧甲基羟乙基纤维素(CMHEC)，或上述混合物。在某些实施方案中，该粘度调节剂的粘度在约20cps至约2000cps范围内。
粘度调节剂的其它的非限制性实施例包括：聚亚烷基氧，某些多糖，聚丙烯酸，聚丙烯酰胺，和上述混合物。该聚亚烷基氧可包括，但不限制于：具有分子量在约1百万至4百万g/mol范围内的聚环氧乙烷。合适的多糖的示意性实施例包括文莱胶、迪坦胶、黄原胶和上述的混合物。聚丙烯酸可具有分子量为约500,000g/mol或更大。
该胶态无机氧化物可以是胶态二氧化硅、胶态氧化铝、胶态氧化锆或上述的混合物。胶态二氧化硅，例如那些来自Nalco Chemical Company的，是在水或其他液体介质中纳米尺寸二氧化硅颗粒的稳定分散体。胶态二氧化硅颗粒尺寸可以是直径在约4至约100纳米范围内。胶态二氧化硅可以被稳定，例如用钠或氨离子，并且可以具有约2至约12范围的pH。
该无机微粒可包括，但不限制于，氧化铝、堇青石(例如堇青石熟料)、莫来石、二氧化钛、钛酸铝、或碳化硅中的至少一种。该无机微粒可选择包括至少一种组分，该组分的热膨胀系数与应用该表面涂层的陶瓷蜂窝基体的热膨胀系数一致。无机微粒的颗粒尺寸可以为约300微米或更小，在某些实施方案中小于约100微米。
该无机粘合剂可包括粘土。该粘土可以是煅烧过的或是未煅烧的，且可以包括但不限于绿坡缕石、球粘土、膨润土、锂蒙脱石、高岭土、蓝晶石、蒙脱石、坡缕石、皂石、海泡石、硅线石或上述的组合。无机粘合剂颗粒尺寸可以是约150微米或更小，在某些实施方案中小于约45微米。
该二次无机纤维可包括但不限于玻璃纤维、沥滤二氧化硅、高氧化铝纤维、莫来石纤维、铝硅酸镁纤维、S-2玻璃纤维、E-玻璃纤维或细(亚微米)直径硅酸铝纤维(HSA)和上述的混合物。
除该二次无机纤维外，在表面涂层配方中可任选包含有机粘合剂纤维。粘合剂纤维的合适实施例包括聚乙烯醇纤维、聚烯烃纤维例如聚乙烯和聚丙烯、丙烯酸纤维、聚酯纤维、醋酸乙烯乙酯纤维、尼龙纤维和上述的组合。基于总组分为以重量计100％，这些纤维适用的量在重量百分比从0至约10范围内。
在表面涂层配方中可任选包括其它有机粘合剂或树脂。合适的有机粘合剂或树脂的实施例包括、但不限制于，水基丙烯酸乳液、丁苯、乙烯基吡啶、丙烯腈、氯乙烯、聚氨酯和类似物。有机硅乳液也适用。其它树脂包括低温、可弯曲热固性树脂例如不饱和聚酯、环氧树脂、和聚乙烯酯(例如聚乙酸乙烯酯或聚乙烯醇缩丁醛乳胶)。至多可使用10％重量百分比的有机粘合剂或树脂。该粘合剂的溶剂，如果需要，可以包括水或对所用粘结剂合适的有机溶剂，例如丙酮。可基于需要的粘合剂载荷和粘合剂系统的可加工性(粘度、固体含量等)，采用常规方法决定粘合剂在溶剂(如果使用)中的溶液浓度。
耐火陶瓷纤维典型地实质上包括氧化铝和氧化硅，并且典型地包含重量百分比约45至约60的氧化铝和重量百分比约40至约55的氧化硅。RCF纤维长度是典型地小于5mm，并且它们的平均纤维直径可在从约0.5μm至约10.5μm范围内。从Unifrax I LLC，Niagara Falls，New York可获得FIBERFRAX耐火铝硅酸盐陶瓷纤维(RCF)。
该术语“生物可溶性无机纤维”是指在生理介质或模拟生理介质例如模拟肺液、生理盐水、缓冲盐溶液或类似物中可充分分解的纤维。该纤维的溶解度可通过测量该纤维在模拟生理介质中作为时间函数的溶解度来测定。也可通过观察在实验动物中直接植入纤维的效果或通过对已经暴露于纤维的动物或人类的检查，即生物抗力，来评价生物可溶性。Unifrax I LLC的美国专利号5,874,375中公开了一种测量纤维在生理介质中的生物可溶性的方法。
另一种评价纤维生物可溶性的方法是基于纤维的组分。例如，德国基于组分系数(KI值)对可呼吸的无机氧化物纤维分级。可通过在无机氧化物纤维中，加和无机氧化物纤维中碱金属和碱土金属氧化物的重量百分比并减去氧化铝重量百分比的两倍，来计算得到该KI值。生物可溶性无机纤维典型地具有的KI值是约40或更大。
非限制性的，可用于制备本文所述表面涂层材料的生物可溶性无机纤维的合适实施例，包括在美国专利号6,953,757；6,030,910；6,025,288；5,874,375；5,585,312；5,332,699；5,714,421；7,259,118；7,153,796；6,861,381；5,955,389；5,928,975；5,821,183和5,811,360中公开的生物可溶性无机纤维，上述每一个文件通过引用结合入本文。
该生物可溶性碱土金属硅酸盐纤维可包括镁氧化物和氧化硅的混合物的纤维化产品，通常称作硅酸镁纤维。该硅酸镁纤维通常包括约60至约90的重量百分比的氧化硅、从大于0至约35重量百分比的氧化镁和5重量百分比或更少的杂质的纤维化产品。依据某些实施方案，该碱土金属硅酸盐纤维包括约65至约86重量百分比的氧化硅、约14至约35重量百分比的氧化镁、0至约7重量百分比的氧化锆和5重量百分比或更少的杂质的纤维化产品。依据其它实施方案，该碱土金属硅酸盐纤维包括约70至约86重量百分比的氧化硅、约14至约30重量百分比的氧化镁和5重量百分比或更少的杂质的纤维化产品。
该生物可溶性无机纤维的示意性实施例包括，但不限于，ISOFRAX
Figure BPA00001403425200051
碱土金属硅酸盐纤维，其具有平均直径在约0.6微米和约2.6微米之间，可从UnifraxI LLC，Niagara Falls，New York获得。市售的ISOFRAX纤维通常包括约70至约80重量百分比的氧化硅、约18至约27重量百分比的氧化镁和4重量百分比或更少的杂质的纤维化产品。
可选择地或可添加地，该生物可溶性碱土金属硅酸盐纤维可以包括钙、镁和硅的氧化物的混合物的纤维化产品。这些纤维通常称作氧化钙-氧化镁-硅酸盐纤维。该氧化钙-氧化镁-硅酸盐纤维通常包括约45至约90重量百分比的氧化硅、从大于0至约45重量百份的氧化钙、从大于0至约35重量百分比的氧化镁和10重量百分比或更少杂质的纤维化产品。
可从Unifrax I LLC(Niagara Falls，New York)的注册商标INSULFRAX下获得市售的氧化钙-氧化镁-硅酸盐纤维。INSULFRAX
Figure BPA00001403425200061
纤维通常包括约61至约67重量百分比的氧化硅、从约27至约33重量百分比的氧化钙和从约2至约7重量百分比的氧化镁的纤维化产品。其它商用氧化钙-氧化镁-硅酸盐纤维包括约60至约70重量百分比的氧化硅、从约25至约35重量百分比的氧化钙，从约4至约7重量百分比的氧化镁，和任选痕量的氧化铝；或，约60至约70重量百分比的氧化硅、从约16至约22重量百分比的氧化钙，从约12至约19重量百分比的氧化镁，和任选痕量的氧化铝。
美国专利号5,346,868、美国专利公开号2007-0020454 A1和国际专利公开号WO/2007/005836中公开了生物可溶性铝酸钙纤维，上述文件通过引用结合入本文。
关于该二次纤维，其它氧化铝/氧化硅陶瓷纤维，例如高氧化铝或莫来石陶瓷纤维，可通过溶胶凝胶方法制备，并且通常包含大于百分之50的氧化铝。一个实施例是FIBERMAX
Figure BPA00001403425200062
纤维，从Niagara Falls，New York的Unifrax I LLC获得。从Owens Corning，Toledo，Ohio可获得市售的氧化镁/氧化铝/硅酸盐纤维例如S2-GLASS。S2-GLASS纤维典型包含从约百分之64至约百分之66的氧化硅、从约百分之24至约百分之25的氧化铝和从约百分之9至百分之10的氧化镁。
沥滤二氧化硅可以以任何方式沥滤并可利用现有技术所知的任何技术。通常，可通过使玻璃纤维经受酸性溶液或其它以适合浸提纤维中的非硅质氧化物和其它组份的溶液，来实现沥滤。美国专利号2,624,658中公开了制备富硅含量的沥滤玻璃纤维的详细描述和方法，该文件的全部公开内容通过引用结合入本文。欧洲专利申请公开号0973697中公开了制备富硅含量沥滤玻璃纤维的另一种方法。
可从BelChem Fiber Materials GmbH，Germany的商标BELCOTEX，HitcoCarbon Composites，Inc.of Gardena California的注册商标REFRASIL，和Polotsk-Steklovolokno，Republic of Belarus的标号PS-23(R)获得浸出玻璃纤维。
在另一个实施方案中，提供一种制造多孔陶瓷(蜂窝)结构体表面涂层的方法，该方法包括形成下列物质的混合物：陶瓷纤维或生物可溶性无机纤维；粘度调节剂；胶态无机氧化物；任选地，无机粘合剂；任选的无机微粒；和任选的二次无机纤维。
在一个实施方案中，在一部分中混合干组份，并且分开地在第二部分中混合湿组份(胶态无机氧化物和水)，之后将两部分混合在一起。在另一个实施方案中，干组份可以以任何次序加入湿组分，并混合。可以干燥该表面涂层材料，例如，在约50°至约100℃干燥约两小时，或直到完全干燥。可在约500-1100℃烧结该干燥的表面涂层材料约1至约5小时，任选加热速率和冷却速率为约100℃/hr或更小。
在废气处理装置的生产中，在烧结该表面涂覆陶瓷蜂窝结构体后，可在包含催化剂的酸性或碱性的溶液或分散液中浸泡该蜂窝体，并随后干燥和再烧结。
在某些实施方案中，提供一种用于多孔陶瓷(蜂窝)基体的表面涂层材料，包括耐火陶瓷纤维或生物可溶性无机纤维；粘度调节剂；胶态无机氧化物；无机粘合剂；无机微粒；和，二次无机纤维。
实施例
在下表1中列出了多种受测表面涂层配方实施例(实施例A、B和C)。测试这些涂层，并与用作DPF表面涂层配方的商用陶瓷糊料产品相比较。
表1
图1显示了与商用陶瓷糊料表面涂层产品相比较的受测表面涂层配方实施例A、B和C的压坯密度测试结果。制备每一种表面涂层材料平板至数毫米的厚度。测量该平板的体积和重量，并计算它们的密度。每一种受测表面涂层配方显示出比商用材料对照样品更高的压坯密度。更高的密度提供了强度和改进的对吸附催化剂涂层材料的抗性。
图2显示了与商用陶瓷糊料表面涂层产品相比较的受测表面涂层配方实施例A、B和C的粘度测试结果。采用标准Brookfield粘度计测量粘度，利用7号转轴转速1rpm。如图所示，该材料的粘度测试可能具有约+/-15％的差异度。然而，每一个例证的受测表面涂层配方显示出比商用材料对照样品更低的粘度。更低的相对粘度允许更容易地泵送该表面涂层配方产品并应用于基体。
图3显示了与商用陶瓷糊料表面涂层产品相比较的受测表面涂层配方实施例A、B和C，在多种条件下处理后的断裂模量(MOR)的测试结果。
热处理实施例A、B和C样品以模拟表面涂层应用条件并模拟催化涂覆步骤中的处理条件(酸碱处理和热处理)。依据ASTM C880进行4点MOR测试。特别是，如图3所示，每个样品各自的第一列显示了当每个样品压坯时测试的MOR测试结果，每个样品的第二列显示了当每个样品热处理后测试的MOR测试结果，每个样品的第三列显示了每个样品热处理、酸/碱(碱性)洗、并第二次烧结后的MOR测试结果。
当在压坯、热处理后，以及酸碱(碱性)处理和第二次热处理后测试，相较于商用材料对照样品，每个受测表面涂层配方显示了更高的断裂模量。
即使在热处理后，相对于比较产品，实施例A、B和C的整体MOR强度更高。实施例B和C配方在热处理后没有显示出重大的MOR强度下降。即使在热处理后存在下降时，相对于比较产品，实施例A、B和C的MOR下降百分比是相当低的。
在热处理后进行酸和碱浸泡处理之后，相对于比较产品，实施例A、B和C的整体MOR强度更高。在热处理后进行酸和碱浸泡处理之后，相对于比较产品，实施例A、B和C的MOR下降百分比是相当低的。
对实施例B和C，测试了其在20和900℃之间的热膨胀系数，分别是36×10-7和40×10-7，与商用陶瓷蜂窝基体一致。
表面涂层配方组份具有以下重量含量：耐火陶瓷纤维或生物可溶性无机纤维，从约15至50％；粘度调节剂，从约0.15至约0.5％；胶态无机氧化物，从约2至约20％；无机微粒，从0至约40％，无机粘合剂(粘土)从0至约10％；二次无机纤维，从0至约10％和，水从约25至约50％。在某些实施方案中，该组分可以具有重量含量：耐火陶瓷纤维或生物可溶性无机纤维，从约20至40％；粘度调节剂，从约0.25至约0.4％；胶态无机氧化物，从约5至约10.5％；无机微粒，从约25至约37％，无机粘合剂(粘土)从约1.5至约5％；二次无机纤维，从约1.15至约5％和，水从约29至约47％。
成功制备了其它表面涂层材料配方，并报道在下表2-5中。
表2
Figure BPA00001403425200091
依据ASTM C880，对如上所述的受测表面涂层配方实施例D和E进行了4点MOR测试。实施例D的压坯MOR是603psi，并且酸/热处理后的MOR是606.5。实施例E的压坯MOR是1147.9psi，并且酸/热处理后的MOR是479.8。
表3
Figure BPA00001403425200101
Figure BPA00001403425200111
Figure BPA00001403425200121
可以理解，本文所述的实施例仅是示意性，并且本领域技术人员可以在不偏离本发明的精神和范围的情况下进行变化和调整。所有的这些变化和调整均落在如上所述的本发明的范围内。进一步，所公开的所有实施方案在可选择范围内不是必须的，因为可以结合本发明的多种实施方案以获得需要的结果。

Claims (22)

1.一种用于多孔陶瓷基体的表面涂层材料，包括：
耐火陶瓷纤维或生物可溶性无机纤维；
粘度调节剂；
胶态无机氧化物；
任选地，无机粘合剂；
任选地，无机微粒；
和，任选地，二次无机纤维。
2.如权利要求1所述的表面涂层材料，其中该耐火陶瓷纤维或生物可溶性无机纤维包括铝硅酸盐纤维、碱土金属硅酸盐纤维或铝酸钙纤维中的至少一种。
3.如权利要求2所述的陶瓷糊料组合物，其中该碱土金属硅酸盐包括硅酸镁或硅酸钙镁中的至少一种。
4.如权利要求1所述的表面涂层材料，其中该无机微粒包括氧化铝、堇青石、莫来石、二氧化钛、钛酸铝或碳化硅中的至少一种。
5.如权利要求1所述的表面涂层，其中该无机粘合剂包括未煅烧粘土或煅烧粘土。
6.如权利要求5所述的表面涂层材料，其中该粘土包括绿坡缕石、球粘土、膨润土、锂蒙脱石、高岭土、蓝晶石、蒙脱石、坡缕石、皂石、海泡石、硅线石或其组合物中的至少一种。
7.如权利要求1所述的表面涂层材料，其中该粘度调节剂包括烷基纤维素聚合物、聚亚烷基氧化物、多糖、聚丙烯酸、聚丙烯酰胺和其混合物中的至少一种。
8.如权利要求1所述的表面涂层材料，其中烷基纤维素聚合物包括甲基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素、羟乙基纤维素、羧甲基纤维素、羟乙基羧甲基纤维素、或羧甲基羟乙基纤维素中的至少一种，或其混合物。
9.如权利要求1所述的表面涂层材料，其中该胶态无机氧化物包括胶态二氧化硅、胶态氧化铝、胶态氧化锆或其混合物中的至少一种。
10.如权利要求1所述的表面涂层材料，其中该二次无机纤维包括玻璃纤维、沥滤二氧化硅纤维、高氧化铝纤维、莫来石纤维、铝硅酸镁纤维、S-2纤维、E-玻璃纤维、玄武岩纤维或细直径硅酸铝纤维中的至少一种。
11.用于多孔陶瓷基体的表面涂层材料，包括：
耐火陶瓷纤维或生物可溶性无机纤维；
粘度调节剂；
胶态无机氧化物；
无机粘合剂；
无机微粒；
和，二次无机纤维。
12.如权利要求11所述的表面涂层材料，包括耐火陶瓷纤维。
13.如权利要求11所述的表面涂层材料，包括生物可溶性硅酸镁纤维。
14.如权利要求11所述的表面涂层材料，包括甲基纤维素粘度调节剂、胶态二氧化硅、无机粘合剂和堇青石微粒。
15.如权利要求14所述的表面涂层材料，其中该无机粘合剂包括煅烧高岭土、膨润土或火山粘土中的至少一种。
16.如权利要求11所述的表面涂层材料，其中该二次无机纤维包括E-玻璃纤维。
17.如权利要求11所述的表面涂层材料，进一步包括有机粘合剂纤维、有机粘合剂或树脂中的至少一种。
18.如权利要求11所述的表面涂层材料包括甲基纤维素粘度调节剂、胶态二氧化硅、无机粘合剂和碳化硅微粒。
19.如权利要求18所述的表面涂层材料，其中该无机粘合剂包括火山粘土。
20.如权利要求1所述的表面涂层材料，进一步包括有机粘合剂纤维、有机粘合剂或树脂中的至少一种。
21.生产多孔陶瓷基体表面涂料的方法，包括形成下列物质的混合物：陶瓷纤维或生物可溶性无机纤维；粘度调节剂；胶态无机氧化物；任选地，无机粘合剂；任选地，无机微粒；和任选地二次无机纤维。
22.如权利要求21所述的方法，其中所述形成混合物包括：
形成下列物质的干混合物：陶瓷纤维或生物可溶性无机纤维；粘度调节剂；任选地，无机粘合剂；任选地，无机微粒；和任选地二次无机纤维；
形成胶态无机氧化物和水的湿混合物；并且
混合所述干混合物和湿混合物。
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